Four fire engines and around 25 firefighters attended a fire at a hotel on Kingston Hill in Kingston-upon-Thames.
A room on the first-floor was destroyed by fire. Two people were taken to hospital by London Ambulance Service.
The fire is believed to have been caused by the failure of an e-bike battery.
A London Fire Brigade spokesperson said: "We encourage anyone who owns an e-bike or e-scooter, or is thinking about purchasing one, to take a look at all of our #ChargeSafe advice on our website to help keep themselves and those around them safer from these types of fires."
"It is vital that you do not store or charge the device on an escape route such as a hallway. Firefighters have attended incidents where people have had to jump from windows or be rescued because their escape route has been blocked by fire or smoke. If it is not possible to keep the device outside or in a shed or garage, make sure it is in a room where you can shut the door and contain a fire.
"When charging your e-bike or e-scooter, make sure you are using the correct charger. Mismatching the charger increases the risk of fire. It's also important not to overcharge and to unplug the charger once it's completed charging. Never charge an e-bike or e-scooter unattended or whilst you're sleeping.
"If you're converting your bike from a pushbike into an e-bike, make sure you get a professional or competent person to carry out the conversion."
The Brigade received the first of five calls about the fire at 0351 and Control Officers mobilised crews from Kingston, Surbiton and New Malden fire stations to the scene. The fire was extinguished by 0533.